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X-Ray Diffraction Studies of Zwitterionic Associating Polymers

  • Y. Shen (a1), C. R. Safinya (a1), L. Fetters (a1), M. Adam (a1), T. Witten (a2), K. S. Liang (a1), R. Chance (a1) and J. Stokes (a1)...

We have carried out x-ray scattering studies in melts of a series of linear polyisoprenes with highly polar sulfo-zwitterion groups at one end. The zwitterion end groups cause aggregation in good solvents for polyisoprene. The aggregation number depends strongly on the molecular weight of the polyisoprene tails and on the polarity of the solvent. Molecular mechanics simulations of the interactions between the zwitterion head groups suggest tubelike or diskline structures for the aggregates. Spherical structures are not energetically favorable. High resolution synchrotron x-ray scattering studies were carried out for six different (chain) molecular weights between 2000 and 23,000. For low molecular weights (between 2000 and 4000) a tubular structure is found with the tubes organized on a well-defined, two-dimensional triangular lattice with very large domain sizes >2000Å. A structural phase transition to a cubic (bcc) phase with long range order is observed to occur for molecular weights >10,000. The lattice spacing increase over the molecular range was between 95Å (for MW-2000) and 206Å (for MW-23,000). For the high molecular weight melts, annealing transforms the structure from (bcc) (with long range order) to an (fcc) disordered structure with short range order.

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1. See, for example, Eisenberg, A., Ions in Polymers: Advances in Chemistry 187; American Chemical Society; Washington, DC, 1980.
2. Davidson, N. S., Fetters, L. J., Funk, W. G., Graessley, W. W., and Hadjichristidis, N., Macromolecules, 21, 112 (1988).
3. Adam, M. and Hadjichristidis, N., unpublished results.
4. Brddas, J. L., Chance, R. R., and Silbey, R., Macromolecules, 21, 1633 (1988).
5. Wang, Z.-G. and Safran, S. A., J. Chem. Phys., 89, 5323 (1988).
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